CN112859518B - Photosensitive dry film and preparation method thereof - Google Patents
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- CN112859518B CN112859518B CN202110005104.1A CN202110005104A CN112859518B CN 112859518 B CN112859518 B CN 112859518B CN 202110005104 A CN202110005104 A CN 202110005104A CN 112859518 B CN112859518 B CN 112859518B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims description 74
- 238000000576 coating method Methods 0.000 claims description 74
- 239000002253 acid Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 30
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 238000004513 sizing Methods 0.000 claims description 28
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000005070 sampling Methods 0.000 claims description 26
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 239000003504 photosensitizing agent Substances 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 16
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 15
- 229920005749 polyurethane resin Polymers 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 12
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 ethylene phthalate diacrylate Chemical compound 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 38
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000013530 defoamer Substances 0.000 description 12
- 230000002411 adverse Effects 0.000 description 11
- 230000004075 alteration Effects 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- MACLACTWFFEZMJ-UHFFFAOYSA-N C(C)(C)C1=CC=CC=2C(C3=CC=CC=C3C(C1=2)=S)=O Chemical compound C(C)(C)C1=CC=CC=2C(C3=CC=CC=C3C(C1=2)=S)=O MACLACTWFFEZMJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses a photosensitive dry film and a preparation method thereof. According to the invention, after epoxy groups on a phenolic resin chain are opened, unsaturated double bonds with photosensitive performance, carboxylic acids with alkali solubility, urethane bonds with a tough structure and ether bonds are respectively introduced at different stages of reaction, and meanwhile, the molecular weight is increased, so that the method is used for preparing the photosensitive dry film, and is beneficial to improving the toughness and resolution of the photosensitive dry film. The photosensitive dry film preparation process provided by the invention has the advantages of simple flow, simple and easily obtained raw materials and relatively low price, and the prepared photosensitive dry film has relatively high toughness and resolution, and the line spacing resolution of the photosensitive dry film can be less than or equal to 0.1mm, so that the production requirement of the current circuit board can be met.
Description
Technical Field
The invention relates to the technical field of photosensitive dry films, in particular to a photosensitive dry film and a preparation method thereof.
Background
The photosensitive dry film is a high molecular functional photoimageable film, has the characteristics of ultraviolet photosensitivity and easy dissolution of alkali liquor, and is used for manufacturing precise circuit board patterns. The manufacture of the circuit board is a complex process which needs a plurality of working procedures and can be finished only by the professional personnel. Wherein, the manufacturing of the circuit pattern only comprises the following steps: firstly, a layer of corrosion-resistant chemical film is covered (screen printed or film-adhered) on a clean copper-clad plate, then the copper-clad plate is exposed by film ultraviolet rays, then developed into a pattern by sodium carbonate solution, unnecessary metal copper is removed by electroplating with electroplating liquid, etching liquid such as ammonium persulfate and the like, finally, the exposed corrosion-resistant film is removed by strong alkali sodium hydroxide solution, the circuit pattern is manufactured, and finally, the next steps of manufacturing of welding resistance, characters, tin spraying, appearance and the like are performed. At present, a great part of manufacturers in the printed circuit board industry also adopt a screen printing mode for manufacturing circuit patterns, namely a photosensitive wet film is printed on a copper-clad plate, and then the photosensitive wet film is dried to expose, develop, electroplate, etch and demold.
However, the conventional method of using a screen printing photosensitive wet film to make a circuit pattern mainly has the following disadvantages: firstly, a high-precision circuit pattern is difficult to manufacture by adopting a printing photosensitive wet film mode, namely, the precision of the wet film is insufficient, and a line distance pattern smaller than 0.15mm is difficult to manufacture; secondly, the production efficiency of the photosensitive wet film is relatively low, and the two steps of baking and electroplating the wet film are needed to be additionally plugged in the manufacturing process, so that the requirements of shortage of human resources and high-energy production are obviously not met; and thirdly, a large amount of energy is consumed during baking of the wet film, a large amount of solution volatilizes during baking of the wet film, and the pollution to the atmosphere is also large. However, if the circuit pattern is manufactured by a film pasting method, two problems exist in the process of manufacturing the circuit pattern by using the photosensitive dry film: firstly, the existing photosensitive dry film mainly depends on imported foreign brands, the price of the photosensitive dry film is generally higher, manufacturers are difficult to reduce the production cost, secondly, the phenomenon that the dry film produced in China is sometimes poor in toughness and low in resolution sometimes exists, for example, the thickness of the dry film is greatly increased because the dry film produced in China is used for reducing the hole breaking rate of a corrosion-resistant film, and the final photosensitive film layer is required to be removed through chemical liquid medicine such as strong alkali and the like, so that the manufacturing of a circuit board is inevitably influenced in some negative ways, the treatment difficulty of wastes is definitely increased, and the emission amount of the wastes is increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of photosensitive resin, wherein the photosensitive resin prepared by the method has unsaturated double bonds with photosensitive performance, alkali-soluble carboxylic acid, urethane bonds and ether bonds with a tough structure, has larger molecular weight, can improve the glass transition temperature of a system, is used for preparing a photosensitive dry film, and is beneficial to improving the toughness and resolution of the photosensitive dry film.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A preparation method of photosensitive resin comprises the steps of adding solvent into a sealed reaction kettle, heating to 90-110 ℃, adding 100 parts by weight of phenolic epoxy resin and 1-5 parts by weight of bisphenol A epoxy resin, adding 31-38 parts by weight of acrylic acid or methacrylic acid after the phenolic epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 0.1-5 parts by weight of catalyst within 30 minutes, keeping the temperature at 110-120 ℃ for 6-15 hours, sampling and detecting the acid value, adding solvent and 50-58 parts by weight of anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 90-110 ℃ for 3-6 hours, sampling and detecting the acid value, adding photosensitive monomer and 1-5 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 90-110 ℃ for 15-60 minutes, adding 10-30 parts by weight of polyurethane resin, finally filtering, discharging and cooling at 90-110 ℃ for 15-60 minutes, and performing polycondensation to obtain the photosensitive resin, wherein the phenolic epoxy resin is at least one of bisphenol F epoxy resin and o-cresol epoxy resin.
Among the above components, the novolac epoxy resin and bisphenol a epoxy resin can improve the skeleton structure of the system, the polyurethane resin and polyethylene glycol diglycidyl ether can provide a tough structure, and acrylic acid or methacrylic acid can provide photosensitivity. The invention optimizes the proportion of each component, and after the epoxy groups on the phenolic resin chain are utilized for ring opening, unsaturated double bonds with photosensitive performance, carboxylic acid with alkali solubility, urethane bonds with a tough structure and ether bonds are respectively introduced at different stages of reaction, and meanwhile, the molecular weight is increased, and the glass transition temperature of the system is improved.
Further, adding a solvent into a sealed reaction kettle, heating to 90-110 ℃, adding 100 parts by weight of phenolic epoxy resin and 1-5 parts by weight of bisphenol A epoxy resin, adding 34-36 parts by weight of acrylic acid or methacrylic acid after the phenolic epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 0.1-5 parts by weight of catalyst within 30 minutes, keeping the temperature at 110-120 ℃ for reaction for 6-15 hours, sampling to detect an acid value, adding the solvent and 50-58 parts by weight of anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 90-110 ℃ for reaction for 3-6 hours, sampling to detect the acid value, adding 3-10 parts by weight of photosensitive monomer and 3-4 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 90-110 ℃ for 15-60 minutes, then adding 20-30 parts by weight of polyurethane resin, keeping the temperature at 90-110 ℃ for 15-60 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin. Experiments show that the photosensitive resin is used for preparing the photosensitive dry film by optimizing the proportion of the components, and the toughness and the resolution of the final photosensitive dry film are improved.
Further, the acid anhydride comprises at least one of maleic anhydride and tetrahydrophthalic anhydride.
Further, the photosensitive monomer comprises at least one of trimethylolpropane triacrylate, pentaerythritol hexaacrylate and ethylene glycol phthalate diacrylate.
Further, the catalyst comprises at least one of N, N-dimethylbenzylamine, N-diethylbenzylamine, ethylenediamine, triethylamine, triethanolamine, N-dimethylethanolamine and triphenylphosphine, and the solvent comprises at least one of a dicarboxylic acid ester DBE and tetramethylene.
The invention also provides the photosensitive resin prepared by the method. The photosensitive resin prepared by the invention has unsaturated double bonds with photosensitive performance, alkali-soluble carboxylic acid, urethane bonds and ether bonds with tough structures, and has larger molecular weight, and the photosensitive resin is used for preparing a photosensitive dry film, thereby being beneficial to improving the glass transition temperature of a system and further enabling the photosensitive dry film to have higher toughness and resolution.
The invention also provides a photosensitive dry film which comprises the photosensitive resin, a photosensitizer, a defoaming agent and a UV quantity indicator.
Further, the photosensitizer comprises at least one of 2-isopropylthioxanthone, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and 4-methylbenzophenone.
The photosensitive dry film has higher resolution, and the line spacing resolution of the photosensitive dry film is less than or equal to 0.1mm.
The invention also provides a preparation method of the photosensitive dry film, which comprises the following steps:
(1) Heating and dissolving a photosensitizer and a UV quantity indicator in a solvent, adding a photosensitive resin and a defoaming agent, uniformly stirring, filtering, and standing;
(2) Coating the sizing material prepared in the step (1) on a PET release film, drying, coating the sizing material with the PE release film, cutting and rolling the PE release film to obtain the photosensitive dry film.
Further, in the step (1), the weight ratio of the photosensitizer, the defoamer and the UV quantity indicator is 10-14:1:0.01.
Further, in the step (1), the solvent comprises at least one of a dicarboxylic acid ester DBE and a tetramethylbenzene;
in the step (2), the coating thickness of the sizing material is 20-50 mu m, and the drying temperature is 90-110 ℃.
In the step (2), a PET heavy release film with the thickness of 18 mu m is selected for coating, and a PE light release film with the thickness of 12 mu m is selected for coating.
In the process of manufacturing the printed circuit board graph, the physicochemical properties of the photosensitive dry film directly influence the excellent degree and precision of the circuit board. The invention aims to enable circuit board manufacturers to easily manufacture precise circuit boards without excessively increasing the production cost, and even reduce the production flow and improve the efficiency. The invention adopts the materials with common market and relatively low price for production, and has higher toughness and resolution.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, after epoxy groups on phenolic resin chains are used for ring opening, unsaturated double bonds with photosensitive performance are respectively introduced at different stages of reaction, carboxylic acids with alkali solubility are provided, urethane bonds and ether bonds with a tough structure are provided, and meanwhile, the molecular weight is increased, and the glass transition temperature of a system is improved;
(2) The photosensitive dry film preparation process provided by the invention has the advantages that the process flow is simple, the raw materials are simple and easy to obtain, the price is low, the prepared photosensitive dry film has higher toughness and resolution, the thickness of the dry film is 30-35 mu m, the diameter of a mask hole can reach 5-6 mm, the line spacing resolution of the photosensitive dry film can reach less than or equal to 0.1mm, and the production requirement of the current circuit board can be met.
Drawings
Fig. 1 is a circuit board obtained by patterning a circuit board using the photosensitive dry film of example 1 and developing the circuit board.
Fig. 2 is a circuit board obtained by using the photosensitive dry film of example 2 to make a circuit board pattern and developing the pattern.
Fig. 3 is a circuit board obtained after the circuit board pattern was formed using the photosensitive dry film of example 3.
Fig. 4 is a circuit board obtained by patterning a circuit board using the photosensitive dry film of example 4 and developing the circuit board.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
The raw materials for the examples and comparative examples are described below:
907 photosensitizer: 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholin-1-one;
ITX: isopropyl thioanthraquinone (2, 4 isomer mixture);
TPO:2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide.
Example 1
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 30 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 2
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 1 part by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 0.1 part by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of dicarboxylic acid ester DBE and 50 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 10 parts by weight of trimethylolpropane triacrylate and 1 part by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 10 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 3
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 5 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 5 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 58 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 5 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 25 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 4
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of bisphenol F novolac epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 34 parts by weight of methacrylic acid after the bisphenol F novolac epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect an acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 4 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 30 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 5
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 4 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 30 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 6
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 5 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 30 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 7
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 110 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 120 ℃ for 6 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 110 ℃ for 3 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 110 ℃ for 1 hour, then adding 10 parts by weight of polyurethane resin, keeping the temperature at 90 ℃ for 60 minutes, finally filtering, discharging and cooling, and performing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Example 8
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 110 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 120 ℃ for 6 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 110 ℃ for 3 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 110 ℃ for 1 hour, then adding 20 parts by weight of polyurethane resin, keeping the temperature at 90 ℃ for 60 minutes, finally filtering, discharging and cooling, and performing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Comparative example 1
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate and 3 parts by weight of polyethylene glycol glycidyl ether when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, and finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin, 30 parts by weight of polyurethane resin and 1 part by weight of defoamer in the step (1), uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Comparative example 2
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 100 parts by weight of tetramethylbenzene into a sealed reaction kettle, heating to 100 ℃, adding 100 parts by weight of o-cresol epoxy resin and 3 parts by weight of bisphenol A epoxy resin, adding 36 parts by weight of acrylic acid after the o-cresol epoxy resin and the bisphenol A epoxy resin are completely dissolved, then dropwise adding 3 parts by weight of N.N-dimethylbenzylamine within 30 minutes, keeping the temperature at 115 ℃ for reaction for 10 hours, sampling to detect the acid value, adding 100 parts by weight of diformate DBE and 52 parts by weight of maleic anhydride when the acid value is less than or equal to 5mgKOH/g, keeping the temperature at 100 ℃ for reaction for 4 hours, sampling to detect the acid value, adding 5 parts by weight of trimethylolpropane triacrylate when the acid value is 60-80 mgKOH/g, continuing to keep the temperature at 100 ℃ for 1 hour, then adding 30 parts by weight of polyurethane resin, keeping the temperature at 100 ℃ for 15 minutes, finally filtering, discharging and cooling, and finishing polycondensation to obtain the photosensitive resin;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
Comparative example 3
The preparation method of the photosensitive dry film comprises the following steps:
(1) Adding 10 parts of acrylic acid, 45 parts of o-cresol formaldehyde epoxy resin, 35 parts of solvent, 0.3 part of catalyst and 0.3 part of hydroquinone into a sealed reaction kettle, heating to 100 ℃ for reaction for 10 hours, adding 8 parts of anhydride, reacting for 5 hours at 105 ℃, adding 1.6 parts of glycidyl methacrylate, and reacting for 4-6 hours at 105 ℃ to obtain photosensitive resin with an acid value of 30-35mgKOH/g and a solid content of about 62%;
(2) Heating and dissolving 6 parts by weight of 907 photosensitizer, 2 parts by weight of ITX, 2 parts by weight of TPO and 0.01 part by weight of UV quantity indicator in a small amount of solvent, adding the photosensitive resin in the step (1) and 1 part by weight of defoamer, uniformly stirring, filtering, and standing for 24 hours to wait for coating;
(3) Coating the sizing material prepared in the step (2) on a PET heavy release film with the thickness of 18 mu m, wherein the coating thickness is 30 mu m, the coating film is required to be smooth and uniform, the coating cannot have adverse phenomena such as chromatic aberration, pinholes, bubbles and the like, drying at the temperature of 100 ℃, baking and drying, taking the phenomenon of no glue flow at the constant temperature of 27 ℃ as the dryness reaching the drying requirement, coating the sizing material by a PE light release film with the thickness of 12 mu m, and cutting and rolling to obtain the photosensitive dry film.
The application method of the photosensitive dry film in the production process of the printed circuit board comprises the following steps of
(1) Film pasting pretreatment: polishing and cleaning the copper-clad plate;
(2) Sticking film, namely sticking the photosensitive dry film on the copper-clad plate by a film sticking machine, wherein the sticking temperature is 105 ℃ to 10 ℃, and the sticking line pressure is 0.55kg/cm;
(3) Exposure: putting the copper-clad plate with the pressed dry film into an exposure machine for exposure, wherein exposure energy is as follows: 120 joules/cm 2, exposure time 10 seconds;
(4) Developing: tearing off the PET film on the exposed copper-clad plate, and then placing the copper-clad plate into a developing machine to develop by using 0.8-1.2 wt% sodium carbonate aqueous solution, wherein the developing temperature is 30 ℃ and the developing speed is 3m/min;
(5) Electroplating: electroplating copper, nickel, zinc and the like according to the requirements of the circuit board;
(6) Etching: etching away the unnecessary copper foil by using chemical liquid medicine;
(7) Removing the film: the photosensitive dry film exposed to ultraviolet rays is removed by using 3 to 5wt% aqueous sodium hydroxide solution.
The photosensitive dry films of examples 1 to 8 and comparative examples 1 to 3 were used for the fabrication of circuit board patterns, exposure was performed using a hole-masking circuit board having a hole diameter of 5mm, the hole-masking performance of the dry films was tested, 100 holes were tested each time, and the hole-breaking rate was counted.
A dry film was laminated on a copper plate by a heated press roller, exposure was performed by using a mask having a wiring pattern with a width of 1:1 of an exposed portion and an unexposed portion, and after development with 1.5 times of the minimum development time, the minimum mask width at which a cured resist line was normally formed was taken as a line pitch resolution.
TABLE 1
| Group of | Porosity (%) | Line distance resolution (mm) |
| Example 1 | 1 | ≤0.1 |
| Example 2 | 9 | ≤0.1 |
| Example 3 | 7 | ≤0.1 |
| Example 4 | 2 | ≤0.1 |
| Example 5 | 3 | ≤0.1 |
| Example 6 | 7 | ≤0.1 |
| Example 7 | 5 | ≤0.1 |
| Example 8 | 3 | ≤0.1 |
| Comparative example 1 | 18 | 0.15-0.2 |
| Comparative example 2 | 15 | 0.15-0.25 |
| Comparative example 3 | 27 | 0.1-0.2 |
As is clear from the results of examples 1 to 8 and comparative examples 1 to 3, after the ring opening of the epoxy group on the phenolic resin chain, unsaturated double bonds having photosensitivity, carboxylic acids having alkali solubility, urethane bonds having a tough structure and ether bonds were introduced at different stages of the reaction, respectively, and used for preparing photosensitive dry films, which is useful for improving toughness and resolution of the photosensitive dry films. As is clear from the results of examples 1 and 5 to 6, the toughness of the photosensitive dry film is better, especially when the weight part of the polyethylene glycol glycidyl ether is 3 to 4 parts; as is clear from the results of examples 1 and 7 to 8, the polyurethane resin was 20 to 30 parts by weight, and the finally obtained photosensitive dry film had good toughness and low porosity.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of photosensitive resin is characterized in that a solvent is added in a sealed reaction kettle and heated to 90-110 ℃, then 100 parts by weight of phenolic epoxy resin and 1-5 parts by weight of bisphenol A epoxy resin are added, 34-36 parts by weight of acrylic acid or methacrylic acid is added after the phenolic epoxy resin and the bisphenol A epoxy resin are completely dissolved, then 0.1-5 parts by weight of catalyst is dropwise added within 30 minutes, the reaction is kept at the constant temperature of 110-120 ℃ for 6-15 hours, sampling is carried out to detect the acid value, when the acid value is less than or equal to 5mgKOH/g, then 50-58 parts by weight of anhydride is added, the reaction is kept at the constant temperature of 90-110 ℃ for 3-6 hours, sampling is carried out to detect the acid value, when the acid value is 60-80 mgKOH/g, 3-10 parts by weight of photosensitive monomer and 3-4 parts by weight of polyethylene glycol glycidyl ether are added, then the constant temperature of 90-110 ℃ is continued for 15-60 minutes, then 20-30 parts by weight of polyurethane resin is added, the constant temperature of 90-110 ℃ is kept for 15-60 minutes, finally filtration, discharging is cooled, and polycondensation is completed, thus obtaining the photosensitive resin, wherein the phenolic epoxy resin is at least one of bisphenol F epoxy resin.
2. The method for producing a photosensitive resin according to claim 1, wherein the acid anhydride comprises at least one of maleic anhydride and tetrahydrophthalic anhydride.
3. The method for producing a photosensitive resin according to claim 1, wherein the photosensitive monomer comprises at least one of trimethylolpropane triacrylate, pentaerythritol hexaacrylate, and ethylene phthalate diacrylate;
The catalyst comprises at least one of N, N-dimethylbenzylamine, N-diethylbenzylamine, ethylenediamine, triethylamine, triethanolamine, N-dimethylethanolamine and triphenylphosphine;
the solvent comprises at least one of a dicarboxylic acid ester DBE and a tetramethylbenzene.
4. A photosensitive resin prepared by the method according to any one of claims 1 to 3.
5. A photosensitive dry film comprising the photosensitive resin of claim 4, a photosensitizer, an antifoaming agent, and a UV quantity indicator.
6. The photosensitive dry film of claim 5, wherein the photosensitizer comprises at least one of 2-isopropylthioxanthone, 2-methyl-1- (4-methylthiophenyl) -2-morpholin-1-one, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 4-methylbenzophenone.
7. The photosensitive dry film of claim 6, wherein the linear distance resolution of the photosensitive dry film is less than or equal to 0.1mm.
8. The method for preparing the photosensitive dry film according to any one of claims 5 to 7, comprising the steps of:
(1) Heating and dissolving a photosensitizer and a UV quantity indicator in a solvent, adding a photosensitive resin and a defoaming agent, uniformly stirring, filtering, and standing;
(2) Coating the sizing material prepared in the step (1) on a PET release film, drying, coating the sizing material with the PE release film, cutting and rolling the PE release film to obtain the photosensitive dry film.
9. The method of producing a photosensitive dry film according to claim 8, wherein in the step (1), the solvent comprises at least one of a dicarboxylic acid ester DBE and a tetramethylene;
in the step (2), the coating thickness of the sizing material is 20-50 mu m, and the drying temperature is 90-110 ℃.
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